Unsymmetrical trisazo dyestuff



' rived from benzene or naphthalene and the lower alkyl, 60 lower alkoxy and chlorinated derivatives thereof, and escanboxyphenyl radical) in which the hydroxyl group is radical, and especially a lower alkyl radical (such as United States Patent ethyl) or a lower hydroxyalkyl radical (such as hydroxymethyl, hydroxyethyl, hydroxypropyl, or hydroxylbutyhor 2,775,582

a lower canboxyalkyl radical (such as canboxymethyil, canboxyethyl, canboxypropyl, carboxybutyl, and prefer- UNSYMMETRICAL TRISAZO DYESTUEF ably carboxymethyl); and

Y represents a sulfo group in the 6- or 7-positionre1'a- Norman L. Anderson, Hamburg, N. Y., assignor to Allied tive to the azo group, that is, in one of the betR-POSIUIOHS Chemical & Dye Corporation, New York, N. Y., a corporation of New York remote from the OX radical, and preferably in the 6-rposition. (#In and other formulae herein the lower No fi g gfggg g 1952 10 alkyl radicals represented by may be the same or different.)

When the dyed fiber is after-treated in the known manner, in the same dyebath or another treatment bath, with 13 Claims. (Cl. 260-173) a water solnble copper "salt or other coppering agent, the Thi i ti l t t unsymmetrical .tris azo dyel5 tast-ness properties of the dyeings are considerably imstufis which produce lblue dyeings on cellulosic fibers the proved, especially against the fading action of light and tastness properties of which dyeings are increased by washing, without substantial change in the shade of the treating with copperinlg agents. It relates more particuyeings. larly to unsymmetrical tris-azo direct dyestuffs for cel- Those dyestuffs in which the oxy-naphthyl sultonic radilil'losi-c fibers in which I-acid imide ('5,5-dihydroxy- 2,Q- c l is a n p h l r i a methoxynaphthyl radical, an dinaphthylamine-7,7-disulfonic acid) is linked by azo h y p y radical or a naphthoxyaeetic radical groups in OTlEhO-tPO'SitlOH to the hydroxyl groups (i. e.,in w ic X in he above formula represents hydrogen, the 6- and 6-positions), on the .one hand, to an aryl nadiy ethyl or carboxvmethyl) are of particular cal and, on the other hand, to a poly-substituted benzene P E Ce, and those in which it is a naphthoxyacetic radiradical having an alkoxy radical in ortho-position to said cal are preferred in view of their exceptional fast-mess to azo group as one su'bstituent and an ortho hydroxylightiflnd t0 Washing carb-oxy-arylazo radical as another su bstituent, with or The ye t fis Of e pre ent invention can he obtained without an alkyl or allcoxy radical as an additional subn various y A simple and advantageous method stitguent, comprises coupling one molecular proportion of I-Iacid I have discovered that certain unsymmetrical trisazo imide dihYdIOXY dinaphfllylamine 5' dyggtufis of id l ih d mfl h i dis-ulfonic acid) with substantially one molecular proporthe and radical is an oxy-naphthyl sulfionic radical which tion of each ot the following diazotized aromatic amines: is linked in the l-position to the azo group and which a POlysubstilllted moflollucleal Emmet-i0 ne contains an oxy radical (a hydroxyl group or an alkoxy s orthohydroxycarboxyarylazo and lower allsoxy or substituted alkoxy radical) in the 2- position and a stituents n the nucleus, and corresponding with the sulfo gnoup in one of the beta-positions remote from the 61151 formula; oxy radical (the 6- or 7-posi-tion)constitute a class of valuable dyestuffs having desirable shade and dyeing properties and producing dyeings on cellulosic rfubers which,

when treated on the fiber with coppering agents, are con- 40 9A1}: verted to coppered derivatives having desirable fastness properties, especially to washing and to light.

Thus, I have discovered that the unsymmetrical trisazo compounds which in the free acid form correspond A with the following Formula I are valuable direct dyestuffs tor. cellulosic fibers; they possess excellent afiinity for natural and artificial cellulosic fibers, such as cotton, viscose and copper rayon, which they dye in clear, bright blue shades:

wherein R, Alk and A have the meaning set out above in connection with Formula I, and (2) a l-amino-Z-oxynaphthalene slrlfionic acid having the sulfo group in one can: on r on OX i Y (I) wherein: I of the beta-positions remote from the oxy radical and R represents an ortho hydroxy-carboxyaryl radical deoorrespondmg with genaml formula:

new Q pecially Ia salicylic acid radical an ortho hydroxyin para-position to the azo group;

Alk represents a lower alkyl radical and especially methyl or ethyl;

A represents hydrogen, Alk or ()Alk, especially methoxy V or ethoxy,. and 1 preferably in ortho-posit-ion to the wherein X and Y have the meaning set out above in conv nection with Formula I. a X represents hydrogen or an alkyl or substituted alkyl The coupling may take place with said diazotized amines inueitherforder. As is usual with :dyestuits of methyl, ethyl, propyl or butyl, and preferably methyl or Patented Dec. 25, 1956' this class, the coupling is carried out in media made al- 3 ktaline with sodium carbonate or bicratbonate, ammonia or-equiva lent alkali.

The polysubstituted mononuclear aromatic amine is preferably a p -salicylazo derivative. of a lower alkoxysubstituted toluidine or phenetidine in which the p-salicylazo radical is para to the amino group and the lower allcoxy radical (having 1 to 4.carbon atoms, preferabl'y methoxy or ethoxy) is ortho to the amino group. Polysubstituted mononuclear aromatic amines. of this type can be obtained, as is wellknown, by diazotizing an..ortho hydroxy-carboxy-arylamine and coupling with a suitable. alkoxy-substituted. mononuclear aromatic amine. Thus, a p-amino-salicy-lic acid (e. g., l-amino- 4-hydroxy-3-benzoic acid or 1-arnino-4-hydroxy-S-methyl- 3-benzoic acid) or; an o-amino-salicylic acid (e. g., 1- amino-2-hydroxy-3-benzoic acid) can be diazotized and coupled with 1-amino=2-methoxy-5-methyl-benzene or 1- amino-2,5-dimethoxy-benzene or 1-amino-2-ethoxy-5- methyl-benzene or 1-amino-2,5-diethoxy-benzene or 1- amino-Z-methoxy (or ethoxy)-benzene or 1-amino-2,5- dipropoxy-benzene or 1-amino-2-propoxy-5-methyl-benzene or 1-amino-2-ethoxy-S-ethyl-benzene. Alternatively, as is wellknown, polysubstituted mononuclear aromatic aminesrof the aforesaid type can be obtained by coupling a suitable diazotized l-amino-3-alkoxy-4-nitrobenzene compound (e. g.-, 1-amino-3-methoxy-6-1nethyl- 4-nitrobenzene) with a suitable ortho-hydroxy-carboxyaryl compound -of the benzene or naphthalene series (e. g., salicylic acid or 2,3-hydroxynaphthoic acid) and reducing. the resulting nitro-monoazo compound to the corresponding amino-compound.

The 1amino-2oxy-naphthalene sulfonic acid may be a 1-amino-2-naphthol-6 or 7-sulfonic acid or salt (e. g., an alkali metal or ammonium salt) or an alkyl, hydroxyalkyl or carboxy-alkyl ether thereof. Preferably it is a lower alkyl, lower hydroxy-alkyl or lower carboxyalkyl ether, and especially one which is a methyl, ethyl orcarboxy-methyl ether.

Desired modifications of shade of dyeings without substantial modification of fastness properties of the dyestuffs can be obtained by employing in the preparation of the dyestuffs a mixture of two or more of the above components which are close homologs; for example, by employing a mixture of 1-amino-S-methyl-Z-methoxybenzene and l-amino--methyl-2-ethoxy-benzene. The invention accordingly includes mixtures of the claimed dyestuffs as well as individual dyestutfs.

The invention will be illustrated by the following specific examples, but it is to be understood that it is not limited to the details thereof and that changes may be madewithout departing from the scope of the invention. The temperatures are in degrees centigradeand the parts are by weight unless designated as parts by no on;

OONS

volume. Where parts are-.by volume, the amount signifies the volume occupied by the same number of parts by weightof water at 4 C. i

H Example 1 An' aqueous paste of p-idiazosalicylic acidwas prepared by'adding 7.2 parts ofsodium nitrite dissolved in 70 It is a blue-black powder, soluble in water-to form blue 30 parts of water to a mixture of 15.3 parts of p-aminosalicylic acid (5-amino-2-hydroxy-benzoic acid), 350 parts of water, 22 parts of B. hydrochloric acid and sufiicient ice to maintain a temperature of 25 to The paste was added to 15.5 parts of ethyl cresidine (1- amino-Z-ethoxy-S-methyl-benzene) which had been dispersed in 400 parts of warm water with the aid of 2 parts of a commercial dispersing agent (Tween 20, a polyoxyalkylene derivative of sorbitan monolaurate) and cooled to 5 with ice. The mixture was further agitated for 2 hours. Ten parts of sodium acetate dissolved in 50 parts of water were then introduced during 2 hours, after which the mixture was agitated at room temperature for 96 hours to carry the coupling reaction to substantial completion. The mixture was rendered acid to Congo red with hydrochloric acid and filtered.

Approximately /2 of the aminomonoazo compound thus obtained (about mol) was mixed with 300 parts of Water and sufficient sodium carbonate (soda ash) to produce a slightly alkaline solution. 3.5 parts of sodium nitrite were added and, after sutficient agitation to dissolve the nitrite, the mixture was poured into an agitated mixture of about 35 parts of 20 B. hydrochloric,

acid and 200 parts of ice to effect diazotization, which was substantially complete after 3 hours. The. diazomonoazo compound thus obtained was introduced during /2 hour into an iced alkaline solution of I-acid imide which Was at 5 and 'had'been prepared from 27.6 parts of I-acid imide, 350 parts of water and 19.5 parts of sodium carbonate. The reaction mixture was agitated for 16 hours at 0 to 5, then heated to salted to 10% by volume with common salt, cooled and filtered. The filter cake was washed with220 parts of 10% aqueous sodium chloride.

The disazo compoundthus obtained was dissolved in a solution of 20 parts of sodium carbonate in 300 parts of water, and the solution was cooled to 0 with 200 parts of ice. An aqueous slurry of diazotized l-amino- 6-sulfo-2-naphthyl ether of hydroxyacetic acid was prepared by adding a slightly alkaline solution, containing 21Lparts of 1-amino-6-sulfo-2-naphthoxyacetic acid, sodium carbonate, 3.5 parts'of sodium nitrite and 200 parts of water, to a mixture of 25 parts of 20 B. hydrochloric acid and 100 'parts of ice. The slurry was added to the agitated-aqueous solution of disazo compound at 0 inan amount sufficient to give a positive test for diazocompound, and the coupling mixture was agitated for"16 hours at 0 to 5. The mixture-Was heated to salted to 10%-by volume, cooled to 30, filtered, dried and ground.

The trisazo dyestuif thus obtained comrespondswith the following formula:

(1)11 CI)H O GHaO OON 75 cellent.

, ExampleZ By employing 14.1 parts of cresidine"in place of the ethyl cres-idine in Example 1, a dyes-tufi was obtained corresponding with the following formula:

by employing 17.9 parts of I-amino-Z-metHoXy-naPhtha lene-G-sulfonic acid'or 16.9 parts of l-aminb-Z-naphthol- 6-su1fonic acid in place of the 1-amino-6-sul-fo-2-naphthoxyacetio acid in Example 2.

t m 0H 0H ocmoooNa v QN: N=N H0 v H: NBOaS NH SOsNa 160ml S OaNa It is a blue-black powder, soluble in water to form blue Iclaim:

solutions, and dyeing cotton bright blue shades which when aftertreated with coppering agents are somewhat redder and possess substantially equal tastness properties as compared with those of the coppered dyestufi of Example 1.

I Example 3 By subs tituting 18.6 parts of l-amino-2,5-diethoxy- 1. An unsymmetrical trisazo dyestuif which dyes cellulosic fibers blue shades the fastness properties of which are improved by aftertreatment of the dyed fiber with coppering agents, said dyestufi in the free acid form corresponding with the general formula:

OAlk OH OH OX wherein: R represents an ontho-hydroxy-carboxyaryl radical derived from :a member of the group consisting of benzene for the ethyl oresidine in Example 1, a dyestufi benzene, naphthalene, and the lower y lower alkoxy,

was obtained corresponding with the following formula:

and chlorinated derivatives thereof, Alk represents a 00in on on ocnioooNa N= QN=N N=N no, ozmo Nada NH- -s0,Na

I oooNa SOaNa It is a blue-black powder, soluble in water to form blue solutions, and dyeing cotton blue shades which when after-treated with coppering agents are a somewhat greener cast than the 'coppered dyeings obtained with the"dye- 4 stufi of Example 1.

Example .4

lower alkyl radical, A represent a member of the group consisting of hydrogen, Alk and OAlk, X represents a member of the group consisting of hydrogen, lower alkyl radicals, lower hydroxyalkyl radicals and lower carboxy- 5 alkyl radicals, and Y represents a sulfo group in one of the beta-positions remote from the OX radical.

2. An unsymmetrical trisazo dyestufli which dyes cellulosic fibers blue shades the fastness properties of which are improved by aftertreatment of the dyed fiber with Y p oy n P 1' D 'l-amino-z-eth yp i coppering agents, said dyestuif in the free acid form corlene-6-sulfonic acid in place ofmthe 1-amino-6-sulfo-2 naphthoxyacetic acid in Example 2, a dyestufi was obtained corresponding with the following formula:

OOH:

OOONa p 1 It is a blue-black powder, soluble in water to form blue solutions, and dyeing cotton blue shades which when aftertreated wit-h copperingagents area somewhat less reddish blue than the coppered dyeings obtained with thejdyestuifof Example 2. i

; OH OH am NaOgS- NH- OaNa responding with the general formula:

0 Alk wherein: Alk represents a lower alkyl radical, A r presents a member of the group consisting of hydrogen, Alk and O C2Ha I NaOgS OAlk, X represents a member of the group consisting of hydrogen, lower alkyl radicals, lower hydroxyalkyl radicals and lower carboxyalkyl radicals, and Y represents a sulfogroup in one of the beta-positions remote from the OX radical.

Dyestuffs possessing similar properties are obtained 3. An unsymmetrical trisazo dyestufl which dyes cellulosic fibers blue shades the fastness properties of which are'improv'ed by aftertreatment ofthe dyedfiber with Alk HOaS wherein: Alk represents a lower alkyl radicaLand Y represents a sulfo group in one of the beta-positions recoppering agents, said dyestuff in the free acid form corresponding with the general formula:

t k r on p on wherein: R represents an orthohydroxy-carboxyaryl radimote from the OCHzCOOH. cal derived from a member of the group consisting of 6. An unsymmetrical trisazo dyestufr which dyes celbenzene, naphthalene, and the lower alkyl, lower alkoxy, lulosic fibers blue shades the fastness properties of which and chlorinated derivatives thereof, Alk represent-s alower 25 are improved by aftertreatment of the dye fiber with alkyl radical, A represents a member of the group concoppering agents, said dyestufi in the free acid form sisting of hydrogen, Alk and OAlk, and Y represents a corresponding with the general formula:

(1)0011 002115 (|)H OH (fQHzCOOH I CH; HOaS- lTT SOaH H l 7. An unsymmetrical trisazo dyestufi which dyes cellulosic fibers blue shades the fastness'pro'p erties of which 4. An unsymmetrical trisazo dyestufi which dyes celluare improved by aftertreatment of the dyed fiber with losic fibers blue shades the fastness properties of which coppering agents, said dyestufi in the free acid form corare improved by aftertreatment of the dyed fiber with 40 responding with the general formula:

sulfo group in one of the beta-positions remote from the OAlkCOOH group.

(IJOOH $911! OH OH OCHRCOOH 0H3 HO3S- III- 80:11 H I 8. An unsymmetrical trisazo dyestufi which dyes celcoppering agents, said'dyestufi in the freeacid form corlulosic fibers blue shades the fastness properties of Which responding with the general formulaz wherein: Alk represents a lower alkyl'radical, A repre- 60 are improved by aftertreatment of the dyed fiber with sents-a memberofthe group consisting of hydrogen, Alk coppen'ng agents, said dyestuff in the free acid form and OAlk, and Y represents a sulfo group in one of the corresponding with the general formula:

, OH I v 1 CH3 HOaS SOsH H I v HOaS wherein n is an integer having a maximum value of 2.

5. An unsymmetrical trisazo dyestufi which dyes eellu- 9. An unsymmetrical trisazo dyestnff which dyes cellosic fibers blue shades the fastness propertiesof which lulosic fibers blue shades the fastnes szpropertiesof which are improved by aftertreatment of the dyed fiber with 75 are improved by aftertreatment of the dyed fiber with beta-positions remote from the OAlkCO0H1group.

9 10 coppering agents, said dyestuif in the free acid form corwherein: Alk represents a lower alkyl radical, X repreresponding with the general formula: sents a member of the group consisting of hydrogen, lower OAlk (1)11 OH 01111: N=NON=N N=l OH I I A H033 --1 II S0311 00011 H wherein: Alk represents a lower alkyl radical, A reprealkyl radicals, lower hydroxy alkyl radicals and lower sents a member of the group consisting of hydrogen, Alk carboxyalkyl radicals, and Y represents a sulfo group in and OAlk, and Y represents a sulfo group in one of the one of the beta-positions remote from the OX radical. beta-positions remote from the OAlk group. 12. An unsymmetrical trisazo dyestufi which dyes cel- 10. An unsymmetrical trisazo dyestufi which dyes cel- 5 lulosic fibers blue shades the fastness properties of which lulosic fibers blue shades the fastness properties of which are improved by Iaftertreatment of the dyed fiber with are improved by aftertreatment of the dyed fiber with coppering agents, said dyestufi in the free acid form corcoppering agents, said dyestufl in the free acid form corresponding with the general formula:

OAlk 0H 0H 0A1k-000H I N=N N=N- N= OH I OAlk 11033 N SOaH 00011 H I I Y responding with the general formula: wherein: Alk represents a lower alkyl radical, and Y repre- OAlk on OH OAlk-OH N=NN= N=N OH I A H038 N 0311 CODE wherein: Alk represents a lower alkyl radical, A represents a sulfo group in one of the beta-positions remote sents a member of the group consisting of hydrogen, 35 m t A1KCOQH group. Alk and OAlk and Y represents a lf group in one of 13. An unsymmetrical trisazo dyestutf which dyes cel- I lulosic fibers blue shades the fastness properties of which the beta posmons remote from the OAlk OH group are improved by aftertreatment of the dyed fiber with 11. An unsymmetrical trisazo dyestuff which dyes celcoppering agents, Said dyestufi in the free acid form lulosic fibers blue shades the fastness properties of which 40 corresponding with the general formula:

OAlk OH OCHa-CO OH on I OAlk 1103s N' som Q I 00 on H are improved by aftertreatment of the dyed fiber with wherein: Alk represents a lower alkyl radical, and Y coppering agents, said dyestufi in the free acid form cor- 50 represents a sulfo group in one of the beta-positions reresponding with the general formula: mote from the OCHz-COOH group.

O Alk OH on ox N=N N=N I o Alk nms- 1TT s on: c 0 0 n H References Cited in the file of this patent UNITED STATES PATENTS 2,270,675 Stein et a1. J an. 20, 1942 2,369,516 Anderau Feb. 13, 1945 FOREIGN PATENTS 268,413 Switzerland Aug. 16, 1950 

1. AN UNSYMMETRICAL TRISAZO DYESTUFF WHICH DYES CELLULOSIC FIBERS BLUE SHADES THE FASTNESS PROPERTIES OF WHICH ARE IMPROVED BY AFTERTREATMENT OF THE DYED FIBER WITH COPPERING AGENTS, SAID DYESTUFF IN THE FREE ACID FORM CORRESPONDING WITH THE GENERAL FORMULA: 